CN116588941B - Method for comprehensively utilizing yellow phosphorus slag - Google Patents

Method for comprehensively utilizing yellow phosphorus slag Download PDF

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CN116588941B
CN116588941B CN202310573712.1A CN202310573712A CN116588941B CN 116588941 B CN116588941 B CN 116588941B CN 202310573712 A CN202310573712 A CN 202310573712A CN 116588941 B CN116588941 B CN 116588941B
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yellow phosphorus
phosphorus slag
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metal oxide
carbon black
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CN116588941A (en
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李法社
刘靖
隋猛
岂慧妮
王霜
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Kunming University of Science and Technology
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Abstract

The invention discloses a method for comprehensively utilizing yellow phosphorus slag, which comprises the steps of adding the yellow phosphorus slag into nitric acid, stirring, reacting, centrifugally separating to obtain waste liquid and a white carbon black precursor, washing, drying, calcining, taking out, cooling and grinding to obtain a white carbon black product; uniformly mixing ammonia water and waste liquid, fully reacting, and then carrying out solid-liquid separation, wherein the obtained liquid is an ammonium nitrate solution, and concentrating and crystallizing to obtain a nitrogenous fertilizer; washing, drying and calcining the solid precipitate obtained by separation, cooling and grinding to obtain a nanoscale composite metal oxide product, and applying the nanoscale composite metal oxide to the field of biomass hydrogen production to improve the hydrogen yield; the invention uses waste yellow phosphorus slag as main raw material, so that the chemical industry solid waste is effectively and comprehensively utilized, and high-performance products are generated, thereby having great significance for comprehensive utilization of resources and environmental protection.

Description

Method for comprehensively utilizing yellow phosphorus slag
Technical Field
The invention relates to the technical field of resource utilization, in particular to a method for comprehensively utilizing yellow phosphorus slag.
Background
Yellow phosphorus slag is an industrial solid waste discharged during yellow phosphorus production by an electrothermal method, a large amount of open-air stacking of the phosphorus slag not only occupies cultivated land, but also causes serious pollution to the environment because harmful elements such as fluorine, phosphorus and the like are gradually dissolved out under the leaching of rainwater. At present, the utilization of the phosphorus slag is mainly combined with the production of the cement industry, but when the phosphorus slag is added into the concrete as a mineral admixture, the early-stage pressure resistance of the concrete is reduced due to the existence of phosphate ions in the phosphorus slag. Therefore, a method for recycling yellow phosphorus slag is not easy to solve.
The process for producing the white carbon black mainly comprises the steps of forming hydrate by SiO 2, wherein the white carbon black is a porous substance, the composition of the white carbon black can be represented by SiO 2·nH2 O, and nH 2 O exists in the form of surface hydroxyl groups and can be dissolved in caustic alkali and hydrofluoric acid and is insoluble in water; white carbon black has excellent properties such as good reinforcing performance, high chemical stability, high temperature resistance, high dispersibility, high wear resistance, insulativity and the like, and can be widely applied to industries such as rubber, printing ink, papermaking, plastics, paint, dye, cosmetics and the like.
At present, the main method for industrially producing the precipitation method white carbon black is a sodium silicate acidification method, generally, sulfuric acid or hydrochloric acid is reacted with water glass, silicic acid is firstly generated, and then the generated silicic acid is further decomposed to prepare the white carbon black. However, the product prepared by the method has low activity, the size of the product particles is not easy to control, and the reinforcing performance is low. Patent application number 202111647850.7 discloses a process for by-producing precipitated white carbon black and light calcium carbonate by utilizing yellow phosphorus waste, but the process is complicated in the preparation process, and the process is not suitable for large-scale production.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention comprehensively utilizes yellow phosphorus slag, respectively prepares white carbon black, nano-scale composite metal oxide and nitrate fertilizer, the prepared nano-scale composite metal oxide is applied to the field of biomass hydrogen production, realizes high-value utilization of the yellow phosphorus slag, selects proper development and utilization directions according to the characteristics of each component part of the yellow phosphorus slag, and realizes clean and environment-friendly production of zero waste, zero waste liquid and zero waste gas in the production process.
The technical scheme of the invention is as follows:
a method for comprehensively utilizing yellow phosphorus slag comprises the following specific steps:
(1) Adding yellow phosphorus slag into nitric acid under the condition of continuous stirring, centrifuging after stirring reaction, carrying out solid-liquid separation to obtain waste liquid and a white carbon black precursor, washing the white carbon black precursor to a pH value of 5-7, drying, calcining, taking out, cooling and grinding to obtain a white carbon black product;
(2) Mixing ammonia water with the mass fraction of 5% -40% with the waste liquid in the step (1) according to the volume ratio of 4-10:1, fully reacting for 30-60 min after uniform mixing, and then realizing solid-liquid separation in a centrifuge, wherein the obtained liquid is an ammonium nitrate solution, and the nitrogen fertilizer is obtained after concentration and crystallization;
(3) Washing the solid precipitate obtained by the separation in the step (2) until the pH value is 11-13, drying, calcining, taking out, cooling and grinding to obtain the nano-scale composite metal oxide product.
The grain diameter of the yellow phosphorus slag in the step (1) is 100-250 mu m; the mass concentration of the nitric acid is 5-40%.
The yellow phosphorus slag in the step (1) is proportioned according to the mass ratio of nitric acid to the yellow phosphorus slag of 10-20:1 according to the amounts of different nitric acid concentrations.
The stirring reaction in the step (1) is carried out for 2 to 5 hours under the condition of continuously stirring at the temperature of 20 to 100 ℃.
When the solid-liquid separation is carried out by the centrifuges in the step (1) and the step (2), the rotating speed of the centrifuges is 3500-5000 r/min, and the centrifuging time is 15-20 min.
The drying temperature of the baking oven in the step (1) and the step (3) is 90-120 ℃, and the drying time of the baking oven is 12-24 hours.
The calcination temperature of the step (1) and the step (3) is 650-800 ℃ and the time is 1-2 h.
The nano-scale composite metal oxide product in the step (3) is used as a catalyst in biomass hydrogen production, and the specific method is as follows: mixing 60-80 g of nano-scale composite metal oxide and biomass according to the mass ratio of 1:1-5, placing the mixture into a furnace, heating the furnace to 600-800 ℃ at a constant heating rate of 15-20 ℃/min, and simultaneously introducing water vapor with the flow rate of 80-320 g/H to prepare hydrogen, wherein the concentration of H 2 can be measured by a gas concentration detector.
The biomass is wood, sugarcane, peanut shells, corn stalks and the like.
The invention has the technical effects that:
1. The method is simple, the characteristics of the components of the yellow phosphorus slag are fully combined to prepare a high-performance product, the utilization of the waste yellow phosphorus slag is improved, white carbon black, nano-scale composite metal oxide and nitrate fertilizer are respectively prepared, and the prepared nano-scale composite metal oxide is applied to the field of biomass hydrogen production and improves the hydrogen yield.
2. The invention realizes clean and environment-friendly production of zero waste, zero waste liquid and zero waste gas in the production process.
Drawings
FIG. 1 is a schematic diagram of the process flow for comprehensively utilizing waste yellow phosphorus slag.
Detailed Description
In order to make the technical scheme and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and examples, but the scope of the present invention is not limited to the above. The yellow phosphorus slag used in the embodiment of the invention is taken from chemical industry limited company of Katsujingjiang tiger in Yunnan, and the yellow phosphorus slag is rich in metal elements such as calcium, silicon, aluminum, magnesium, iron and the like.
Example 1
A method for comprehensively utilizing yellow phosphorus slag is shown in fig. 1, and comprises the following steps:
(1) Diluting 100mL of 68% by mass of concentrated nitric acid with water to prepare a 20% by mass nitric acid solution, and grinding waste yellow phosphorus slag into powder with the particle size of 125 mu m in a grinder;
(2) Adding the nitric acid diluted in the step (1) into yellow phosphorus slag according to the mass ratio of the nitric acid to the yellow phosphorus slag of 10:1 under the condition of continuous stirring, continuously stirring at 100 ℃ for reaction for 4 hours, and centrifuging in a centrifuge at the rotating speed of 3500r/min for 20min to separate waste liquid and white carbon black precursors;
(3) Washing the white carbon black precursor in the step (2) with deionized water to a pH value of 7, drying at 120 ℃ for 12 hours, calcining at 750 ℃ for 1 hour, taking out, cooling, and grinding to obtain a white carbon black product, wherein the whiteness of the white carbon black product is 84.1%, and the purity is 98.8%;
(4) Mixing ammonia water with the mass concentration of 5% and the waste liquid in the step (2) according to the volume ratio of 4:1, fully reacting for 60min after completely mixing, centrifuging for 15min at the rotation speed of 5000r/min, and realizing solid-liquid separation in a centrifuge, wherein the obtained liquid is ammonium nitrate solution, and nitrogen fertilizer can be obtained through concentration and crystallization, and the obtained solid is a composite metal oxide precursor; (5) Washing the composite metal oxide precursor in the step (4) with deionized water to a pH value of 11, drying at 120 ℃ for 12 hours, calcining at 750 ℃ for 1 hour, taking out, cooling, and grinding to obtain a nanoscale composite metal oxide product, wherein the CaO content is 72.9%, the Al 2O3 content is 12.5%, the MgO content is 5.5%, and the Fe 2O3 content is 0.51%, and the balance is unavoidable impurities; (6) The prepared nano-scale composite metal oxide is applied to biomass hydrogen production, 80g of the nano-scale composite metal oxide is mixed with sugarcane according to the mass ratio of 1:4 and is put into a tube furnace, the furnace is heated to 700 ℃ at a constant heating rate of 15 ℃/min, water vapor with the flow rate of 160g/H is introduced in the reaction process, hydrogen is obtained, the proportion of H 2 in four gases H 2、CO、CO2、O2 is measured through a gas concentration detector, and the highest concentration of H 2 in the reaction process is 67.2%.
Comparative example 1
320G of sugarcane is put into a tube furnace, the furnace is heated to 700 ℃ at a constant heating rate of 15 ℃/min, during the reaction process, 160g/H of water vapor is introduced into the flow position to obtain hydrogen, and the proportion of H 2 in four gases H 2、CO、CO2、O2 is measured by a gas concentration detector, so that the highest concentration of H 2 in the reaction process is 23.2%.
From a comparison of example 1 and comparative example 1, it can be seen that the addition of the composite metal oxide prepared in example 1 can significantly improve the yield of hydrogen.
Example 2
A method for comprehensively utilizing yellow phosphorus slag comprises the following steps:
(1) Diluting 100mL of 68% by mass of concentrated nitric acid with water to prepare a 5% by mass nitric acid solution, and grinding waste yellow phosphorus slag into 100 mu m-diameter powder in a grinder;
(2) Adding the nitric acid diluted in the step (1) into yellow phosphorus slag according to the mass ratio of the nitric acid to the yellow phosphorus slag of 20:1 under the condition of continuous stirring, continuously stirring at 20 ℃ for reaction for 5 hours, and centrifuging in a centrifuge at the rotating speed of 5000r/min for 15min to separate waste liquid and white carbon black precursors;
(3) Washing the white carbon black precursor in the step (2) with deionized water until the pH value is 5, drying at 90 ℃ for 24 hours, calcining at 800 ℃ for 1 hour, taking out, cooling, and grinding to obtain a white carbon black product, wherein the whiteness of the white carbon black product is 80%, and the purity is 88%;
(4) Mixing ammonia water with the mass concentration of 40% and the waste liquid in the step (2) according to the volume ratio of 10:1, fully reacting for 30min after completely mixing, centrifuging for 20min at the rotating speed of 3500r/min, and realizing solid-liquid separation in a centrifuge, wherein the obtained liquid is ammonium nitrate solution, and nitrogen fertilizer can be obtained through concentration and crystallization, and the obtained solid is a composite metal oxide precursor;
(5) Washing the composite metal oxide precursor in the step (4) with deionized water to a pH value of 13, drying at 90 ℃ for 24 hours, calcining at 650 ℃ for 2 hours, taking out, cooling, and grinding to obtain a nanoscale composite metal oxide product, wherein the CaO content is 70.8%, the Al 2O3 content is 14.3%, the MgO content is 6.5%, and the Fe 2O3 content is 0.52%, and the balance is unavoidable impurities;
(6) The prepared nano-scale composite metal oxide is applied to biomass hydrogen production, 60g of heavy nano-scale composite metal oxide is mixed with sugarcane according to the mass ratio of 1:1 and is put into a tube furnace, the furnace is heated to 800 ℃ at a constant heating rate of 20 ℃/min, water vapor with the flow rate of 320g/H is introduced in the reaction process, hydrogen is obtained, the proportion of H 2 in four gases H 2、CO、CO2、O2 is measured by a gas concentration detector, and the highest concentration of H 2 in the reaction process is 66.8%.
Example 3
A method for comprehensively utilizing yellow phosphorus slag comprises the following steps:
(1) Diluting 100mL of 68% by mass of concentrated nitric acid with water to prepare a 20% by mass nitric acid solution, and grinding waste yellow phosphorus slag into powder with the particle size of 250 mu m in a grinder;
(2) Adding the nitric acid diluted in the step (1) into yellow phosphorus slag according to the mass ratio of the nitric acid to the yellow phosphorus slag of 15:1 under the condition of continuous stirring, continuously stirring at 60 ℃ for reaction for 3 hours, and centrifuging in a centrifuge at the rotating speed of 4000r/min for 18min to separate waste liquid and white carbon black precursors;
(3) Washing the white carbon black precursor in the step (2) with deionized water to a pH value of 6, drying at 100 ℃ for 15 hours, calcining at 800 ℃ for 1 hour, taking out, cooling, and grinding to obtain a white carbon black product, wherein the whiteness of the white carbon black product is 85%, and the purity is 90%;
(4) Mixing ammonia water with the mass concentration of 20% and the waste liquid in the step (2) according to the volume ratio of 5:1, fully reacting for 45min after completely mixing, centrifuging for 18min at the rotating speed of 4000r/min, and realizing solid-liquid separation in a centrifuge, wherein the obtained liquid is ammonium nitrate solution, and nitrogen fertilizer can be obtained through concentration and crystallization, and the obtained solid is a composite metal oxide precursor; (5) Washing the composite metal oxide precursor in the step (4) with deionized water to reach a pH value of 11, drying at 100 ℃ for 16 hours, calcining at 650 ℃ for 2 hours, taking out, cooling, and grinding to obtain a nanoscale composite metal oxide product, wherein the CaO content is 73.1%, the Al 2O3 content is 11.7%, the MgO content is 4.5%, and the Fe 2O3 content is 0.48%, and the balance is unavoidable impurities; (6) The prepared nano-scale composite metal oxide is applied to biomass hydrogen production, 70g of the nano-scale composite metal oxide and sugarcane are mixed according to the mass ratio of 1:2 and are placed into a tubular furnace, the furnace is heated to 600 ℃ at a constant heating rate of 18 ℃/min, 80g/H of water vapor is introduced in the reaction process to obtain hydrogen, the proportion of H 2 in four gases H 2、CO、CO2、O2 is measured through a gas concentration detector, and the highest concentration of H 2 in the reaction process is 63.2%.
Example 4
A method for comprehensively utilizing yellow phosphorus slag comprises the following steps:
(1) Diluting 100mL of 68% by mass of concentrated nitric acid with water to prepare 40% by mass of nitric acid solution, and grinding waste yellow phosphorus slag into powder with the particle size of 200 mu m in a grinder;
(2) Adding the nitric acid diluted in the step (1) into yellow phosphorus slag under the condition of continuously stirring according to the mass ratio of the nitric acid to the yellow phosphorus slag being 16:1, continuously stirring at 80 ℃ for reaction for 3 hours, and then centrifuging in a centrifuge at the rotating speed of 5000r/min for 15min to separate waste liquid and white carbon black precursors;
(3) Washing the white carbon black precursor in the step (2) with deionized water to a pH value of 7, drying at 90 ℃ for 24 hours, calcining at 650 ℃ for 2 hours, taking out, cooling, and grinding to obtain a white carbon black product, wherein the whiteness of the white carbon black product is 82%, and the purity is 89%;
(4) Mixing ammonia water with the mass concentration of 30% and the waste liquid in the step (2) according to the volume ratio of 4:1, fully reacting for 30min after completely mixing, centrifuging for 20min at the rotating speed of 3500r/min, and realizing solid-liquid separation in a centrifuge, wherein the obtained liquid is ammonium nitrate solution, and nitrogen fertilizer can be obtained through concentration and crystallization, and the obtained solid is a composite metal oxide precursor; (5) Washing the composite metal oxide precursor in the step (4) with deionized water to a pH value of 12, drying at 120 ℃ for 12 hours, calcining at 800 ℃ for 1 hour, taking out, cooling, and grinding to obtain a nanoscale composite metal oxide product, wherein CaO content is 75%, al 2O3 content is 13.8%, mgO content is 5.6% and Fe 2O3 content is 0.54%, and the balance is unavoidable impurities;
(6) The prepared nano-scale composite metal oxide is applied to biomass hydrogen production, 60g of the nano-scale composite metal oxide is mixed with sugarcane according to the mass ratio of 1:5 and is put into a tube furnace, the furnace is heated to 800 ℃ at a constant heating rate of 20 ℃/min, water vapor with the flow rate of 320g/H is introduced in the reaction process, hydrogen is obtained, the proportion of H 2 in four gases H 2、CO、CO2、O2 is measured through a gas concentration detector, and the highest concentration of H 2 in the reaction process is 57.2%.
The experiment is carried out by changing the biomass sugarcane into wood, peanut shells and corn stalks in the embodiment, and the highest concentration of H 2 in the reaction process is as follows: 43.3 to 55.8 percent, 49.8 to 62.7 percent and 40.5 to 53.8 percent, and the hydrogen production rate in the experimental process can be obtained: sugarcane is more than peanut shell is more than wood is more than corn straw.
The foregoing is only a partial, but not all embodiments of the present invention, and any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be covered by the scope of the claims of the present invention.

Claims (8)

1. A method for comprehensively utilizing yellow phosphorus slag is characterized by comprising the following specific steps:
(1) Under the condition of continuously stirring, adding yellow phosphorus slag into nitric acid, carrying out solid-liquid separation after stirring reaction to obtain waste liquid and a white carbon black precursor, washing the white carbon black precursor until the pH value is 5-7, drying, calcining, taking out, cooling and grinding to obtain a white carbon black product;
(2) Uniformly mixing ammonia water with mass fraction of 5% -40% with the waste liquid in the step (1) according to the volume ratio of 4-10:1, fully reacting for 30-60 min, and then carrying out solid-liquid separation, wherein the obtained liquid is an ammonium nitrate solution;
(3) Washing the solid precipitate obtained by the separation in the step (2) until the pH value is 11-13, drying, calcining, taking out, cooling and grinding to obtain a nanoscale composite metal oxide product;
the nano-scale composite metal oxide product is used as a catalyst in biomass hydrogen production, and the specific method is as follows: mixing 60-80 g of nano-scale composite metal oxide and biomass according to the mass ratio of 1:1-5, heating to 600-800 ℃ at the heating rate of 15-20 ℃/min, and simultaneously introducing water vapor with the flow rate of 80-320 g/h to prepare the hydrogen.
2. The method for comprehensively utilizing the yellow phosphorus slag according to claim 1, wherein the particle size of the yellow phosphorus slag in the step (1) is 100-250 μm; the mass fraction of the nitric acid is 5% -40%.
3. The method for comprehensively utilizing yellow phosphorus slag according to claim 1, wherein the mass ratio of nitric acid to yellow phosphorus slag in the step (1) is 10-20:1.
4. The method for comprehensively utilizing yellow phosphorus slag according to claim 1, wherein the stirring reaction in the step (1) is carried out at 20-100 ℃ for 2-5 hours.
5. The method for comprehensively utilizing yellow phosphorus slag according to claim 1, wherein the rotational speed of a centrifugal machine is 3500-5000 r/min and the centrifugal time is 15-20 min during solid-liquid separation in the step (1) and the step (2).
6. The method for comprehensively utilizing yellow phosphorus slag according to claim 1, wherein the drying temperature in the step (1) and the drying temperature in the step (3) are 90-120 ℃ and the drying time is 12-24 hours.
7. The method for comprehensively utilizing yellow phosphorus slag according to claim 1, wherein the calcining temperature in the step (1) and the calcining temperature in the step (3) are 650-800 ℃ and the calcining time is 1-2 h.
8. The method for comprehensively utilizing yellow phosphorus slag according to claim 1, wherein the biomass is wood, sugarcane, peanut shells or corn stalks.
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